Dentifrices



March 4, 1969 K. w. GYARMATHY ETAL 3,431,339

DENTIFRICES Filed July 20, 1966 INVENTORS. KENNETH WILLIAM GYARMATHY BYALEXANDER WILLIAM BOUCHAL ATTORNEY United States Patent 3,431,339DENTIFRICES Kenneth W. Gyarmathy, Old Bridge, and Alexander W.

Bouchal, Westfield, N.J., assignors to Colgate-Palmolive Company, NewYork, N.Y., a corporation of Delaware Filed July 20, 1966, Ser. No.566,610

US. Cl. 42452 12 Claims Int. Cl. A61k 7/16 ABSTRACT OF THE DISCLOSUREDental tablet for use in place of toothpaste. The tablet contains anintimate blend of water-soluble, anticaries fluorine containing agents,such as stannous fluoride or sodium monofluorophosphate, polishingagent, such as agent including insoluble sodium metaphosphate, foamingagent, such as sodium lauryl sulfate, and releasable matrix, such aswaxy polyethylene glycol.

The present invention relates to dentifrices.

Toothpastes are, of course, the most commonly used dentifrices but, asgenerally employed, they do not ac complish as thorough a cleaning ofthe teeth as is desirable. One problem arises through carelessness inbrushing, particularly a lack of thoroughness in brushing posteriorteeth. This is the location where caries occur most frequently.

In addition, while toothpastes containing anticaries agents such asstannous fluoride have been widely used, it has been found that theactivity of the added agent may diminish substantially on storagedepending upon the particular formulation.

It is therefore an object of this invention to provide a dentifricewhich promotes more thorough cleaning of the posterior teeth onbrushing.

Another object of this invention is the provision of a dentifricecontaining an anticaries agent which is resistant to loss of activity inthe dentifrice on storage.

Other objects of this invention will be apparent from the followingdetailed description and claims. In this description and claims, allproportions are by weight unless otherwise indicated.

In accordance with one aspect of this invention, there is provided aunique compressed dental tablet for use, with a toothbrush, in place oftoothpaste. The tablet, which contains an intimate blend of awater-soluble, anticaries fluorine containing agent, polishing agent,foaming agent and releasable matrix, has upper and lower convexsurfaces, has a thickness at its thickest point of about 3 to 20 mm.,has a Stokes hardness of about 2.5 to 6.0 kg. The size, shape andconsistency of the tablet are such that it is readily crushed betweenthe teeth and, when so crushed, breaks up to form simultaneously amultiple combination of (a) powdery material which is released to formwith the saliva a slurry containing a nonpalpable polishing agent andwhich has the effect of a toothpaste slurry and (b) larger, palpable,gritty fragments of the tablet. The tablet has a pH of about 4.5-6.5when slurried in water at 20% concentration. We have found that thissubstantially improves the cleaning of the lingual surfaces. Thus, incomparative tests, the use of the dental tablet of this invention gave aconsiderably better removal of plaques and debris from the lingualsurfaces than was obtained by the use of toothpaste.

The tablet preferably has straight sides and has a length of about 8 mm.to 20 mm., a width of about mm. to 13 mm. and the maximum depth of theconvexly curved top and bottom is preferably about to 25% of the tabletwidth. Advantageously it is oblong, most preferably oval. The preferredtablet will be oblong in shape so as to better fit between the posteriorteeth when used.

A preferred form of tablet in accordance with this invention isillustrated in the drawing, in Which ITIGURE l is the top view of thetablet, drawn to sea e;

FIGURE 2 is a side view of the tablet, drawn to scale;

FIGURE 3 is a cross-sectional view taken along the line 3-3 of FIGURE 1;

FIGURE 4 is a view showing the tablet just before it is crushed betweenthe teeth.

In accordance with this invention there is provided a crushable dentaltablet containing a water-soluble, anticaries fluorine containing agentsuch as stannous fluoride, sodium monofluorophosphate or sodium fluoridein combonation with polishing agent, forming agent, a releasable matrix,all in a substantially anhydrous form. The amount of moisture in thetablet should preferably not exceed about 1%. We have found that theanticaries agent in such a dry tablet retains its effectiveness onstorage for very long periods of time, in sharp contrast to thedeterioration which takes place in toothpaste.

In a preferred embodiment of the invention, the tablet contains theanticaries fluorine containing agent, a stabilizer for the anticariesfluorine containing agent, a surface active foaming agent, a releasablematrix, and an agent to promote disintegration and a gelling agenttogether with a flavoring agent and an absorbent for the flavoringagent.

The preferred active anticaries ingredients are stannous fluoride andsodium monofluorophosphate, which are preferably supplied in finelydivided form, e.g., having a particle size in the range of about 880microns to 1,800 microns. This is considerably finer than the materialconventionally employed in making toothpaste where a coarse agent, suchas stannous fluoride, is dissolved in water. The amount of anticariesagent in the tablet may be varied but should provide an effective,nontoxic amount containing above 0.01% fluoride ppm.) per tablet. Themaximum fluoride content of the tablet is typically about 1%. Thepreferred fluoride content is about 0.076 to 0.3%, say 0.1%. Thusstannous fluoride, when employed, would be typically in amount of about0.04 to 4.1%, preferably about 0.3 to 1.24%, say 0.4%. Sodiummonofluorophosphate, when employed, would be typically in amount ofabout 0.076 to 7.6%, preferably about 0.57 to 2.3%, say 0.76%. It iswithin the scope of this invention to use other active ingredientstogether with the anticaries fluorine-containing agent such as stannousfluoride or sodium monofluorophosphate. Examples of such ingredients arequaternary ammonium salts such as diisobutylphenoxyethoxyethyl dimethylammonium chloride. In addition urea may be employed in certain of thecompositions when packaged in moisture retardant packages.

The preferred polishing agents are insoluble phosphate salts, mostpreferably the insoluble sodium metaphosphate which has been found to becompatible with Water-soluble, anticaries fluorine-containing agent.Other specific polishing agents include insoluble potassiummetaphosphate, calcium pyrophosphate, magnesium orthophosphate,trimagnesium phosphate, tricalcium phosphate and dicalcium phosphatedihydrate, calcium carbonate, anhydrous dicalcium phosphate and alumina.It is also within the broader scope of the invention to employ otherdental cleaning abrasives, which will not scratch the enamel surface ofthe teeth or abrade the dentin, such as calcium or magnesium carbonate,particularly when active ingredients other than fluorides are used inthe tablet.

This invention permits the use of combinations of fluorides andpolishing agents which heretofore were not used in toothpaste. Manypolishing agents. contain calcium and cannot be used in fluoridecontaining toothpastes because the calcium reacts with the fluoride saltand reduces the available fluorine. Thus, where cost of polishing agentis of importance, it is possible to select the cheapest polishing agentfor a far larger group of compounds and to use the polishing agent as apowder. The average particle size of the polishing agent may be the sameas that usually employed for dentifrices, e.g., in the range of about 2to 6 microns, preferably 3.5 to microns, with about 99.9% of thepolishing agent passing a standard 200 mesh sieve which has openingsabout 0.074 mm. in diameter and well over 95%, typically 99%, passing astandard 325 mesh sieve (which has openings about 0.044 mm. indiameter). The amount of polishing agent in the composition isadvantageously in the range of about to 95%, preferably about 50 to 85%.

Insoluble sodium metaphosphate often contains a soluble impurity,soluble sodium trimetaphosphate. In order to avoid certain undesirableeffects of the sodium trimetaphosphate, it is preferable to include inthe composition a material which inactivates or neutralizes this solubleimpurity such as anhydrous dicalcium phosphate. Other suitableinactivators would be any of the slightly soluble magnesium or aluminumphosphates. A suitable proportion of the anhydrous dicalcium phosphateis up to about 5% by weight of the insoluble sodium metaphosphate.

The foaming agent in the composition may be any of those surface activeagents employed as detergents and sudsing agents in dentifrices.Water-soluble sulfates of compounds having long chain alkyl radicals(e.g., chains of 10 to 18 carbon atoms) are suitable. One preferredmaterial is a long chain fatty acid rnonoglyceride sulfate, such as thesodium salt of hydrogenated coco fatty acid rnonoglyceride sulfate usedalone or in combination with sodium lauryl sulfate. Other suitablematerials are the fatty acid amides of amino acids such as sodiumN-lauroyl sarcosinate. The proportion of the detergent is advantageouslyin the range of about l-10%.

The releasable matrix in the composition is a binder which serves tounite the fine particles of the composition into a coherent mass whenthe composition is compressed as a tablet. A particularly suitablebinder is a waxy polyethylene glycol, such as a polyethylene glycol ofaverage weight of about 300 to 8,000, e.g. the products sold as Carbowax6000 and Carbowax 4000. In the manufacture of the tablets we have foundit highly advantageous to supply the binder ingredient in a finelydivided solid condition, e.g., in the form of fine particles which willpass a US. Standard 80 mesh screen (which has openings about 0.177 mm.in diameter) and preferably a 100 mesh screen (which has openings about0.149 mm. in diameter). Particularly good results have been obtained, inthe manufacturing procedure, by bringing the fine binder particles intocontact with the much more finely divided polishing agent before thesubstantial addition of the other ingredients of the composition. Inplace of the waxy polyethylene glycol, other waxy material such astristearin, paraflin and the like may be used. The amount of binder isadvantageously in the range of about 420% of the composition.

The preferred compositions of this invention also contain a small amountof a gelling or thickening agent which helps to produce a stronger foamon brushing. Suitable gelling agents are generally natural and syntheticgums and gumlike materials, such as sodium carboxymethyl cellulose,Irish Moss, gum tragacanth, gum acacia, gelatin, sodium alginate, methylcellulose, polyvinyl-pyrroli done and the like. The proportion ofgelling agent in the composition is advantageously in the range of up toabout 2%.

The stability of the stannous fluoride in the composition may beenhanced by the inclusion of tetrasodium pyrophosphate, advantageouslypresent in proportions in the range of about 0.1% to 0.4% based on theweight of the composition. Less preferably, other nontoxic sequesteringagents may be employed together with, or in place of, the tetrasodiumpyrophosphate.

The final disintegration of the tablet in the saliva is promoted by thepresence of small amounts of starch, e.g., in amounts up to about 4%,that, about 0 to 4%, preferably about 2 to 3%, Arrowroot starch, cornstarch, purified cellulose, olginic acid, methyl cellulose and the likeare particularly suitable for this purpose.

Any suitable flavoring oils, e.g. menthol or oils of Spearmint,peppermint, Wintergreen or fruit flavors alone or in combination, may beused in the composition in amount suflicient to give the desired flavor,generally less than about 2%. The flavor oil is desirably absorbed on afinely divided flavor retainer. A preferred flavor retainer is veryfinely divided silica (e.g., having a particle size of under one micron,and a correspondingly large surface area). Other flavor retainers, knownin the art, may also be used, e.g., the natural gums such as gum karayaand gum arabic. Microcrystalline cellulose has also given good resultsas a flavor retainer. The amount of flavor retainer to be used is inpart dependent on the amount of flavoring agent in the composition; ingeneral the amount of flavor retainer is about 0.5 to 3.0%.

To contribute desirable sweetness to the taste of the flavor, asweetening agent such as sodium saccharin or sodium, potassium andcalcium alts of cyclohexylsulf-amic acid is advantageously added inamounts up to about 0.67%.

It is advantageous to include a lubricant in the composition to aid inits processing in the tabletting machinery. Talc is excellent for thispurpose. Magnesium and calcium stearate are also suitable. Theproportion of lubricant is generally in the range of about 0.1 to 5% byWeight.

In the preferred compositions of this invention, mannitol is included.This ingredient aids in the disintegration of the table-t in the salivaof the mouth and improves the smoothness of the tablet duringdisintegration, thereby permitting the tablet to melt readily in themouth. It also enhances the flavor and sweetness of the mixture. Theamount of mannitol is advantageously in the range of up to 50% of thecomposition.

The inclusion of finely divided cellulose in the composition, in amountsup to about 10%, enhances the effect of the binder and also aids in thedisintegration of the tablet in the saliva of the mouth. It also servesas a filler.

Suitable coloring agents may be incorporated in the mixture for estheticeffect. The moisture content of the tablet is desirably less than about1%, e.g. about 0.5 to 1.0%. Preferably the tablet when made into a 20%solids slurry will have a pH of 5 .06.0.

In the manufacture of the tablet it is advantageous to first blend theinsoluble powdered abrasives or polishing agents and the powderedreleasable matrix binder in a powder mixer, than add the water solubleanticaries fluorine-containing powder together with the foaming agent,all in dry condition, to the mixer. A stabilizer for the anticariesagent and a gelling agent may also be blended together with theanticaries agent and the foaming agent. The flavoring agent, sweetener(e.g., saccharin) and flavor retainer may then be separately blended toform a dry powdery mass which is then blended thoroughly in the powdermixer with the previously mentioned mixed ingredients. Thedisintegrators and fillers, in dry, powdered condition, may then beincorporated. Prior to tabletting the powdered talc may be mixedthoroughly with the powder. The mixture is then fed to a suitable tabletpress, such as a rotary tablet press, where it is compressed at apressure high enough to produce a tablet of the desired hardness,generally about 350-l,400 kg./sq. cm. In the case of the preferredcompositions, this pressure is about 1,125 kg./sq. cm.

In accordance with certain aspects of this invention, the preferredtablet contains a unit dosage for dental use, say about 500550 mg,typically about 520 mg.

EXAMPLE 1 The tablet was made up of the following composition.

Ingredients: Parts by weight Insoluble sodium metaphosphate(microcrystalline powder of food grade purity) 61.13 Anhydrous dicalciumphosphate (microcrystalline powder, food grade purity, meeting NFXIpurity limits) 6 Polyethylene glycol having an average molecular weightof 6,000-7,500 (Carbowax 6000) 10 F.C. & C. Blue #1 Lake (Blue #1, 10%

precipitated on alumina substrate 0.017 F.D. & C. Violet #1 Lake (Violet#1, 10%

precipitated on alumina substrate) 0.017 Stannous fluoride 0.4Tetrasodium pyrophosphate 0.4

Sodium salt of hydrogenated coco fatty acid monoglyceride sulfate 2Sodium lauryl sulfate Sodium carboxymethylcellulose (CMC-7 MP) 1.25Silica (particle size 0.015-0.020 micron, Cab- O-Sil M-S) 1.25 Flavoringoil Sodium saccharin 0.325 Finely divided woodpulp cellulose (Solka FlocBW 100) 5.475 Mannitol (Nil?) 5 Arrowroot starch 2.5 Alabama talc(U.S.P.) 2

The ingredients were blended in the manner previously described andcompressed in a tabletting machine at a pressure of 1,125 kg./ sq. cm.to produce tablet slugs. The slugs were crushed through an 8-12 U.S.standard mesh screen (having openings 2.38-1.68 mm. in diameter) and theresulting granules were tab'letted at 1,125 kg./ sq. cm. to producetablets having a Stokes hardness of 3-4.5 kgs. Each tablet had thedoubly convex shape 4 illustrated in the drawing (which is drawn toscale) and was 0.127 cm. long and 0.0724 cm. wide and, at its thickestpoint, Was 0.0524 cm. thick. Each tablet had a circumferentialstraight-sides surface band (reference numeral 3) 0.0318 cm. in height,whose straight sides 4 were parallel to the short (thickness) axis ofthe tablet.

EXAMPLE 2 The tablet was made up of the following composition.

6 Ingredients: Parts by weight Tetrasodium pyrophosphate 0.4 Sodium saltof hydrogenated coco fatty acid monoglyceride sulfate 2 Sodium laurylsulfate 0.5 Sodium carboxymethylcellulose (CMC-7 MP) 1.25 Silica(particle size 0015-0020 micron, Cab- O-Sil M-5) 1.25 Flavoring oil 1.75Sodium saccharin 0.325 Finely divided woodpulp cellulose (Solka Floc BW100) 5.475 Mannitol (N.F.) 5 Arrowroot starch 2.5 Alabama talc (-U.S.P.)2

The tablets were made in the manner previously described by blending,compressing at 1,125 kg./sq. cn1., crushing, and tabletting at 1,125kg/sq. cm. thereby obtaining tablets having a Stokes hardness of 3-4.5'kgs. Each tablet had the doubly convex shape illustrated in the drawing(which is drawn to scale) and was 0.127 cm. long and 0.0724 cm. wideand, at its thickest point, was 0.0524 cm. thick. Each tablet had acircumferential straight-sides surface band (Reference numeral 3) 0.0318cm. in height, whose straight sides were parallel to the short(thickness) axis of the tablet.

When the tablets of each of the examples are used, the average usernaturally bites down on it with the posterior teeth, usually crushingthe tablet between the .first molar and either a bicuspid or anothermolar. The

dentifrice then follows the usual food paths in and around the posteriorteeth. The bits and pieces formed (together with powder) when thedentifrice is crushed make the user more apt (than when toothpaste isused) to clean away food debris that collects in the interproximals andalong gingival margins. Because the user feels the presence of theseparticles he tends to continue brushing until the particles are removed.In this way the user is automatically encouraged to brush the buccalsurfaces of posterior teeth and the lingual surfaces of all teeth, andthus to clean more thoroughly the areas where caries occur mostfrequently.

In addition, the fluoride-containing tablets of this invention havedemonstrated much better retention of their content of active materialon storage than fluoride-containing toothpaste.

Although the present invention has been described with reference toparticular embodiments and examples, it will be apparent to thoseskilled in the art that variations and modifications of this inventioncan be made and that equivalents can be substituted therefor withoutdeparting from the principles and true spirit of the invention.

We claim:

1. A dental tablet crushable with the teeth into powdery materialcontaining a polishing agent and larger palpable, gritty fragments foruse in the brushing of teeth with a toothbrush comprising an intimateblend of watersoluble, anticaries, fluorine-containing agent selectedfrom the group consisting of stannous fluoride and sodiummonofiuorophosphate in an amount to provide a fluorine content in saidtablet of about 0.01% to 1% by weight, about 20% to 95% by weight of apolishing agent, about 1% to 10% by Weight of foaming agent, and about4% g to 20% of waxy releasable matrix selected from the group consistingof a polyethylene glycol, tristearin and paraffin; said tablet having amoisture content up to about 0.01% to about 1% by weight, said tablethaving upper and lower convex surfaces, a thickness at its thickestpoint of about 3 to 20 'mm. and a Stokes hardness of about 2.5 to 6.0kgs.; said tablet having a pH of about 4.5 to 6.5 when slurried in waterat 20% concentration.

2. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said tablet further comprises about 0.1% to0.4% by weight of a stabilizer for said water-soluble anticariescontaining agent, up to about 4% by weight of an agent to promotedisintegration, up to about 2% by weight of a gelling agent, less thanabout 2% of a flavoring agent and about 0.5 to 3.0% of an absorbent forsaid flavoring agent.

3. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said watersoluble anticariesfluorine-containing compound is stannous fluoride.

4. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said waxy releasable matrix is a polyethyleneglycol.

5. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said tablet has a length of about 8 mm. to 20rnnr, a width of about 5 mm. to 13 mm. and the maximum depth of theconvexly curved top and bottom is preferably about to 25% of the widthof said tablet.

6. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said tablet contains a unit dosage for dentaluse and comprises about 0.49 to 0.55 mg. of fluorine provided by saidwatersoluble, anticaries fluorine-containing compound, about 331.6 to366.5 :mg. of said polishing agent, about 12.35 to 13.65 mg. of saidfoaming agent and about 49.3 to 54.7 mg. of said releasable matrix.

7. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said fluorine content of said tablet is about0.076 to 0.3% by weight.

8. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 7 wherein said watersoluble anticariesfluorine-containing compound is sodium monofluorophosphate.

9. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said polishing agent is a powdered insolublephosphate salt having an average particle size of about 2 to 6 microns.

10. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 9 wherein said polishing agent comprises sodiummetaphosphate and anhydrous dicalcium phosphate, said anhydrousdicalcium phosphate being present in amount up to 5% by weight of saidsodium metaphosphate.

11. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 1 wherein said foaming agent is a surface activedetergent.

12. A dental tablet for use in brushing of teeth with a toothbrush asclaimed in claim 11 wherein said surface active detergent is selectedfrom the group consisting of sodium N-lauroyl sarcosinate, sodium laurylsulfate, and the sodium salt of hydrogenated coco fatty acidmonoglyceride sulfate.

References Cited UNITED STATES PATENTS 834,676 10/1906 Luyties 16793840,738 1/1907 Barnard 16793 3,116,208 12/1963 Emond 167-93 3,227,6171/1966 Manahan et a1.

RICHARD L. H'UFF, Primary Examiner.

U.S. C1. X.R. 42457, 49

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,431,339 March 4, 1969 Kenneth W. Gyarmathy et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below:

In the heading to the printed specification, lines 3 and 4, "Kenneth W.Gyarmathy, Old Bridge, and Alexander W. Bouchal, Westfield, N. J."should read Kenneth William Gyarmathy, Old Bridge, and Alexander WilliamBouchal, Westfield, N. J.

Signed and sealed this 7th day of April 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

